JP7139558B2 - chlorine dioxide generating aerosol - Google Patents

Description

The present invention relates to an aerosol product that generates chlorine dioxide.

Chlorine dioxide ClO ₂ has a strong oxidizing power and is used as a disinfectant, virus remover, and deodorant. Chlorine dioxide is generally used in the form of an aqueous solution from the viewpoint of handling, but its stability is problematic. Therefore, it is used in the form of a so-called stabilized chlorine dioxide aqueous solution, which is in the form of a chlorite such as sodium chlorite and has an alkaline pH.
As a means for continuously releasing chlorine dioxide gas at a constant concentration using such a stabilized chlorine dioxide aqueous solution, a chlorine dioxide liquid agent having dissolved chlorine dioxide gas, chlorite and a pH adjuster as constituent components is used. It has been proposed (for example, Patent Document 1).

Japanese Patent No. 3110724

The chlorine dioxide solution disclosed in Patent Document 1 can continuously release chlorine dioxide gas at a constant concentration for a constant period of time. However, the present inventors have found that such a chlorine dioxide solution is insufficient from the viewpoint of generating highly effective chlorine dioxide.
From the viewpoint of immediate effect, a means of separately preparing a chlorite such as sodium chlorite and an activator such as citric acid for activating it and generating chlorine dioxide and mixing them before use. is also conceivable, but once mixed, the immediate effect is lost over time.
An object of the present invention is to solve the above problems. That is, the object is to provide an aerosol product capable of continuously generating highly effective chlorine dioxide.

The present invention includes a first container filled with a first liquid, a second container filled with a second liquid, and a propellant, and an aerosol product having a discharge mechanism for discharging and mixing the first liquid and the second liquid. and
the first liquid comprises an aqueous chlorite solution;
The second liquid relates to an aerosol product, characterized in that it contains an aqueous acidic substance solution.

According to the present invention, it is possible to provide an aerosol product capable of continuously generating highly effective chlorine dioxide.

Schematic diagram showing an example of an aerosol product in a double structure container Schematic diagram showing an example of an actuator in a double structure container Schematic diagram of double can aerosol product Example of petri dish installation for virus titer comparison test

The present invention includes a first container filled with a first liquid, a second container filled with a second liquid, and a propellant, and an aerosol product having a discharge mechanism for discharging and mixing the first liquid and the second liquid. and
the first liquid comprises an aqueous chlorite solution;
The second liquid is characterized by containing an acidic substance aqueous solution.

The aerosol product of the present invention discharges and mixes a first liquid containing an aqueous solution of chlorite and a second liquid containing an aqueous solution of an acidic substance. When the chlorite aqueous solution and the acidic substance aqueous solution are mixed, the chlorite aqueous solution is activated to generate chlorine dioxide. That is, in the present invention, since generation of chlorine dioxide starts immediately after ejection, chlorine dioxide can be generated from the ejection target portion with high immediate effect (at a high rate of generation). For example, viral titers can be reduced within an hour after ejection.
In addition, since the immediate effect is high, compared with the conventional chlorine dioxide liquid agent using the stabilized chlorine dioxide aqueous solution, it is less likely to be affected by organic matters in the ejection target portion.
The first liquid containing the chlorite aqueous solution and the second liquid containing the acidic substance aqueous solution are filled in the first container and the second container, respectively, in the aerosol product except during discharge, so they are in a stable state. can exist in Therefore, it is possible to continuously generate highly effective chlorine dioxide.

Materials that can be used in the present invention are described below.
<Chlorite aqueous solution>
In the present invention, an aqueous solution of chlorite is used as the first liquid. Chlorite has at least one selected from the group consisting of sodium chlorite, potassium chlorite, lithium chlorite, calcium chlorite, magnesium chlorite, barium chlorite, etc. is preferred. Sodium chlorite, potassium chlorite, and lithium chlorite are more preferred, and sodium chlorite is even more preferred. A commercially available sodium chlorite aqueous solution may be used, for example, Pyuologen (Biocide Japan Co., Ltd.).
A buffering agent or the like may be added to the chlorite aqueous solution, if necessary.
The concentration of the chlorite aqueous solution in the aerosol product is not particularly limited because it also depends on the concentration of the acidic substance aqueous solution used at the same time. More preferably 100,000 ppm, even more preferably 20 to 10,000 ppm.
The pH of the chlorite aqueous solution is not particularly limited because it depends on the chlorite used and the buffering agent used as necessary, but from the viewpoint of stability, it is preferably 5 or more and 12.5 or less. It is preferably 5 or more and 12 or less, more preferably 5 or more and less than 9, and particularly preferably 5 or more and less than 8. When the aqueous chlorite solution contains a buffer, for example, it is preferably 5 or more and 12 or less, more preferably 5 or more and less than 9, even more preferably 5 or more and 8.5 or less, and 5 More than 8 and less than 8 are particularly preferable.

<Aqueous solution of acidic substance>
In the present invention, an aqueous solution of an acidic substance is used as the second liquid. The acidic substance is not particularly limited as long as it can activate the chlorite aqueous solution. Acidic substances include acids such as hydrochloric acid, sulfuric acid, nitric acid, phosphoric acid, lactic acid, acetic acid, succinic acid, oxalic acid, citric acid, boric acid, and gluconic acid; It is preferred to have at least one selected from the group consisting of salts such as disodium hydrogen. More preferably, it is at least one selected from the group consisting of hydrochloric acid, sulfuric acid, citric acid and lactic acid.
From the viewpoint of safety to the human body, acids such as phosphoric acid, lactic acid, succinic acid, oxalic acid, citric acid, boric acid, and gluconic acid, sodium citrate, sodium dihydrogen phosphate, and disodium hydrogen phosphate It is preferable to have at least one selected from the group consisting of salts such as More preferably, it is at least one selected from the group consisting of citric acid and lactic acid.
The concentration of the acidic substance aqueous solution is not particularly limited, but is preferably 0.1 to 30% by mass, more preferably 1 to 20% by mass, even more preferably 1 to 5% by mass. The pH is preferably 1-5, more preferably 1-3.

In the present invention, it is preferable that the first liquid is an aqueous sodium chlorite solution and the second liquid is an aqueous citric acid solution. By mixing sodium chlorite and citric acid, for example, chlorine dioxide can be generated by the following reaction.
_{5NaClO2 + 4C5H7O5 (} COOH)
→4ClO ₂ +2H ₂ O+5Na ⁺ +C ₅ H ₇ O ₅ COO ⁻

<Other additives>
Other additives may be used in the aerosol product of the present invention to the extent that they do not impair the effects of the present invention. For example, known surfactants, thickeners, fragrances and the like can be added. From the viewpoint of stability, the additive is preferably contained in the second liquid. In the present invention, since the containers in which the first liquid and the second liquid are filled are separate, the mixed solution of the first liquid and the second liquid can be obtained while maintaining the stability of the chlorite as the first liquid. It is possible to give the effect of an additive to

<Propellant>
The propellant is not particularly limited, and liquefied gas or compressed gas may be used. Compressed gas is preferable, and examples thereof include nitrous oxide gas, nitrogen gas, carbon dioxide gas, and mixed gas thereof.

<Aerosol products>
The aerosol product of the present invention comprises a first container filled with a first liquid and a second container filled with a second liquid. Any container form may be used as long as the first liquid and the second liquid are filled separately and the two can be discharged and mixed.
The double structure container is, for example, an outer container comprising a propellant filling space filled with a propellant, a first container, and a second container, and a first liquid and a second liquid from the first container and the second container. It has a discharge mechanism for discharging and mixing the liquid, and the filling space for the propellant is formed between the first container, the second container and the outer container.
The double structure container has an outer container comprising a propellant filling space filled with a propellant, a first container filled with a first liquid, and a second container filled with a second liquid. By the pressure of the propellant filled in the propellant filling space, the first liquid and the second liquid can be simultaneously discharged and mixed from the first container and the second container.

An example of a double structure container including a discharge mechanism will be described below with reference to the drawings.
FIG. 1 is a schematic diagram showing an example of an aerosol product in a double structure container, and FIG. 2 is a schematic diagram showing a cross section of an actuator (discharging mechanism) in the double structure container of FIG.
This double structure container 10 includes a metal pressure-resistant container (outer container) 11 provided with an aerosol valve 12 . Inside the pressure-resistant container (outer container) 11 are a first inner bag 15A that defines a first container for filling the first liquid, and a second container that defines a second container for filling the second liquid. Two inner bags 15B are provided. Further, a propellant filling space 16 for filling a propellant is formed by a gap between each of the pressure-resistant container (outer container) 11, the first inner bag 15A and the second inner bag 15B.
Further, the aerosol valve 12 includes a first stem 14A and a second stem 14A having stem passages therein, which are arranged to be vertically slidable in the first housing 13A and the second housing 13B, respectively. stem 14B is provided. A common actuator (ejection mechanism) 21 is provided at the upper ends of the first stem 14A and the second stem 14B.

In FIG. 1, components located inside the pressure vessel 11 and the actuator 21 are indicated by dashed lines.
In the aerosol product of the present invention, it is preferred that the dispensed mixture is dispensed in the form of a mist. The structure of the actuator for discharging in the form of mist is not particularly limited, and a known structure can be used. For example, the following aspects are mentioned.

The common actuator 21 includes a first actuator passage 22A that communicates with the stem passage of the first stem 14A, a second actuator passage 22B that communicates with the stem passage of the second stem 14B, and these first actuator passages. An L-shaped mixing space 23 is provided which communicates with the actuator passage 22A and the second actuator passage 22B at one end and communicates with the discharge port 24A of the injection port forming member 24 at the other end. The mixing space 23 is provided with a swirl passage 23A having a function of dividing the first liquid and the second liquid into fine droplets while passing through them.
By adopting such a discharge mechanism, the pressure of the propellant filled in the propellant filling space causes the first liquid and the second liquid to mist from the first inner bag 15A and the second inner bag 15B, respectively. It can be discharged and mixed in a shape.

In FIG. 1, an aspect of discharging and mixing two types of content liquids, the first liquid and the second liquid, has been described, but in a double structure container, three or more types of content liquids may be discharged and mixed. That is, by further providing a third inner bag, a third housing, a third stem, etc. in the pressure container 11, three or more types of content liquids can be discharged and mixed. For example, a third inner bag or a fourth inner bag may be provided, filled with the above-mentioned other additives, etc., and discharged and mixed. Thereby, each solution can be kept stable.
In addition, although the inner bags are arranged in parallel in FIG. 1, various known arrangements of the inner bags can be adopted. The first inner bag and the second inner bag may be arranged vertically. For example, the first inner bag may be arranged on top and the second inner bag may be arranged on the bottom, and the actuator and the first inner bag and the second inner bag may be connected by a tube or the like. The tube that connects the second inner bag and the actuator may be passed outside the first inner bag, or may be passed inside the first inner bag so as not to come into contact with the first liquid.

On the other hand, the double-can type is a mode in which two aerosol products are integrated, and the first liquid and the second liquid are simultaneously discharged and mixed by a propellant.
For example, a first inner container filled with the first liquid, a second inner container filled with the second liquid, a first outer container in which the first inner container is stored, and a second inner container in which the second inner container is stored Having two outer containers and a discharge mechanism for discharging and mixing the first liquid and the second liquid,
Spaces formed between the first inner container and the first outer container and between the second inner container and the second outer container are each filled with a propellant.

FIG. 3 is a schematic diagram of a dual-can aerosol product.
The aerosol product 30 comprises a first outer container 31 a , a second outer container 31 b and an actuator (dispensing mechanism) 36 with an actuator passageway 35 . A first inner container 32a is stored in the first outer container 31a, and the first inner container 32a is filled with a first liquid. A second inner container 32b is stored in the second outer container 31b, and the second inner container 32b is filled with a second liquid. The first outer container 31 a and the second outer container 31 b are fixed by a fixed platen 37 .
In the aerosol product, between the first outer container 31a and the first inner container 32a and between the second outer container 31b and the second inner container 32b, a first propellant filling space 33a and a second propellant are provided. The propellant filling spaces 33 b are respectively formed, and the propellant filling spaces are filled with a propellant for discharging the first liquid and the second liquid from the discharge mechanism 35 .
Although the containers are arranged in parallel in FIG. 3, the containers can be arranged in various known manners. For example, the first outer container and the second outer container may be arranged vertically. The first outer container may be arranged above and the second outer container may be arranged below, and the actuator may be connected to the first outer container and the second outer container by a tube or the like.

The discharge mechanism 35 has discharge ports for discharging and mixing the compositions filled in the first inner container 32a and the second inner container 32b. The first liquid and the second liquid ejected from the ejection port are preferably ejected in the form of mist.
A dual-can type aerosol product may also be in a mode of discharging and mixing three or more types of content liquids in the same manner as the double-structured container. That is, by further providing a third outer container, a third inner container, a third propellant filling space, etc., it is possible to discharge and mix three or more types of content liquids.

The actuator (ejection mechanism) in FIG. 3 has two ejection ports, and the first liquid and the second liquid are ejected (preferably in the form of mist) from separate ejection ports and mixed. In this way, the first liquid and the second liquid may be mixed after being ejected from the actuator (ejection mechanism).
The structure of the actuator (discharge mechanism) is not particularly limited in both the double structure container and the double can type. For example, as shown in FIG. 2, the first liquid and the second liquid may be mixed in an actuator (ejection mechanism) and then ejected (preferably in the form of mist), or as shown in FIG. may be provided, and the first liquid and the second liquid may be discharged from separate discharge ports (preferably in the form of mist) and mixed. The former is more preferable from the viewpoint of the reactivity of the first liquid and the second liquid.

In the aerosol product of the present invention, the mixing ratio (mass of the first liquid: mass of the second liquid) of the first liquid and the second liquid discharged from the actuator (discharging mechanism) is the concentration of the first liquid and the second liquid. Although it is not particularly limited because it depends on the ratio, it is preferably 0.8:1.2 to 1.2:0.8.

<container>
The container (inner container) filled with the first liquid and the second liquid is not particularly limited. A container made of known resin, metal, or a combination thereof can be used.
The outer container is not particularly limited as long as it can withstand the pressure of the propellant, and known metals and the like can be used.

The present invention will be specifically described below with reference to examples. However, the present invention is not limited to the aspects of the following examples.

<Example 1: Production of aerosol product 1>
The following aqueous solutions were prepared as the first liquid and the second liquid, and filled in the first container and the second container of the double structure container as shown in FIG. 1, respectively. Nitrogen gas was filled in the gap formed between the outer container, the first container and the second container of the double structure container to obtain an aerosol product 1. The ejection mechanism was designed to eject the mixture in the form of mist as shown in FIG. 2, and the ejection amounts of the first liquid and the second liquid were 1:1 on a mass basis. The chlorite ion concentration after ejection is 500 ppm.
(first liquid)
・Sodium chlorite aqueous solution (chlorite ion concentration 1000 ppm, pH 8.9)
Diluted Pyuorogen (Biocide Japan Co., Ltd.) (Second liquid)
・20% by mass aqueous solution of citric acid

<Comparative Example 1>
Cleverin Spray (Taiko Pharmaceutical Co., Ltd.), which is a commercially available chlorine dioxide preparation, was used.

<Comparative Example 2>
An aerosol container was filled with the same sodium chlorite aqueous solution (chlorite ion concentration: 500 ppm, pH: 8.7) as used in Example 1 to obtain a comparative aerosol product. Nitrogen gas is used as the propellant, and the spray form is mist.

<Virus coated petri dish>
A feline calicivirus (FCV-F9) diluted with phosphate-buffered saline was coated on a petri dish and dried to prepare a virus-coated petri dish.

<Virus titer comparison test>
Using the virus-coated petri dishes prepared as described above, the effects of the chlorine dioxide agents of Examples and Comparative Examples were investigated. Product spraying took place in a garage 95 cm wide, 180 cm long and 160 cm high. A test table 1 with a height of 60 cm was prepared in a garage, and a virus-coated petri dish 3 was placed as shown in FIG. sprayed. The amount of spray was the same for each chlorine dioxide agent.
At 0 and 1 hour after spraying, the dish was removed from the garage, virus was extracted, and the virus titer was evaluated. Each chlorine dioxide agent was evaluated after 0 hour and 1 hour, and the arithmetic mean value was calculated and evaluated. Table 1 shows the results.
Viral titer was evaluated by the _TCID50 method. The results of each example are shown when the value in the case of using distilled water as an injection sample is set to 100.
From the results in Table 1, it can be seen that the aerosol product of the present invention has a high immediate effect.

<Titration test of available chlorine dioxide>
The change in the effective chlorine dioxide concentration of each sodium chlorite aqueous solution over time was confirmed by the following method.
・Measurement sample liquid 1 (without citric acid)
Purogen (Biocide Japan Co., Ltd.) was diluted with purified water and adjusted to 500 ppm, which can be measured with a BCI titration kit.

・Measurement sample solution 2 (activated with 1% by mass aqueous solution of citric acid)
Pyuorogen (Biocide Japan Co., Ltd.) was diluted with purified water to prepare a 2,000 ppm Pyuorogen diluted solution. Separately, a 1% by mass aqueous solution of citric acid was prepared. 20 g each of a 2,000 ppm diluted solution of Pyuologen and a 1% by mass aqueous solution of citric acid were mixed to prepare a 1,000 ppm diluted solution of activated Pyuologen. This was further diluted two-fold and adjusted to 500 ppm, which can be measured by BCI kit titration, to obtain measurement sample liquid 2.

・Measurement sample solution 3 (activated with 10% by mass aqueous solution of citric acid)
Pyuorogen (Biocide Japan Co., Ltd.) was diluted with purified water to prepare a 2,000 ppm Pyuorogen diluted solution. Separately, a 10% by mass aqueous solution of citric acid was prepared.
20 g each of a 2,000 ppm diluted Pyuologen solution and a 10 mass % aqueous citric acid solution were mixed to prepare a 1,000 ppm activated Pyuologen diluted solution. This was further diluted twice and adjusted to 500 ppm measurable with a BCI titration kit to obtain measurement sample liquid 3.

・Measurement sample liquid 4 (activated with a 20% by mass aqueous solution of citric acid)
Pyuorogen (Biocide Japan Co., Ltd.) was diluted with purified water to prepare a 2,000 ppm Pyuorogen diluted solution. Separately, a 20% by mass aqueous solution of citric acid was prepared. 20 g each of a 2,000 ppm diluted solution of Pyuologen and a 20% by mass aqueous solution of citric acid were mixed to prepare a 1,000 ppm diluted solution of activated Pyuologen. This was further diluted two-fold and adjusted to 500 ppm measurable with a BCI titration kit to obtain measurement sample liquid 4.

○ Titration procedure Titration was carried out as follows using a BCI titration kit (Biocide Japan Co., Ltd.).
1. Add 10 drops of C/D Reagent#1 to the titration vessel.
2. Add 10 drops of C/D Reagent#2 to container 1.
3. Add 1 g of the measurement sample solution to the container of 2 and mix.
4. Add 5 drops of C/D Reagent#3 to the 3 container.
5. Add one drop of C/D Reagent#4 to the container in step 4 and add until the liquid becomes clear.
Each measurement sample was titrated immediately after sample solution preparation (day 0), after 3 hours (after 0.125 days), after 1 day, after 3 days, and after 35 days.
○ Calculation method of effective chlorine dioxide From the results of titration, effective chlorine dioxide concentration was calculated by the following formula. Table 2 shows the results.
Effective chlorine dioxide (ppm) = number of drops x 5
From the results in Table 2, it was found that the effective chlorine dioxide of the sodium chlorite aqueous solution hardly changed unless citric acid was added, and that the addition of citric acid decreased it over time. That is, compared to products of the type in which an active agent such as citric acid is mixed with chlorite, the aerosol product of the present invention can stably generate chlorine dioxide with high immediate effect without being affected by time. I understand.

Next, changes over time in the effective chlorine dioxide concentration were confirmed when hydrochloric acid or sulfuric acid was used.
・Measurement sample solution 5 (activated with 1% by mass hydrochloric acid aqueous solution)
Pyuorogen (Biocide Japan Co., Ltd.) was diluted with purified water to prepare a 2,000 ppm Pyuorogen diluted solution. Separately, a 1% by mass hydrochloric acid aqueous solution was prepared. 20 g each of a 2,000 ppm diluted solution of Pyuologen and a 1% by mass hydrochloric acid aqueous solution were mixed to prepare a 1,000 ppm diluted solution of activated Pyuologen. This was further diluted two-fold, adjusted to 500 ppm measurable by BCI kit titration, and used as measurement sample solution 5.

・Measurement sample liquid 6 (activated with a 1% by mass sulfuric acid aqueous solution)
The purogen was diluted with purified water to prepare a 2,000 ppm diluted solution of purogen. Separately, a 1% by mass aqueous solution of sulfuric acid was prepared. 20 g each of a 2,000 ppm diluted solution of purogen and a 1 mass % aqueous solution of sulfuric acid were mixed to prepare a 1,000 ppm diluted solution of activated purogen. This was further diluted two-fold and adjusted to 500 ppm measurable by BCI kit titration to obtain measurement sample liquid 6.

・Measurement sample solution 2 (activated with 1% by mass aqueous solution of citric acid)
A measurement sample liquid 2 prepared in the same manner as described above was used.

The measurement sample solution was titrated immediately after sample preparation (0 days), 3 hours (0.125 days), 1 day, 3 days, and 35 days after sample preparation. Sample solutions 5 and 6 were also run after 9 days and 28 days. Titration was performed in the same manner as above using a BCI titration kit (Biocide Japan Co., Ltd.) to calculate effective chlorine dioxide concentration ppm. Table 3 shows the results.
From the results below, it can be seen that when a strong acid such as hydrochloric acid or sulfuric acid is used as an activator, the active ingredient is quickly deactivated. It can be seen that the aerosol product of the present invention can stably generate highly effective chlorine dioxide without being affected by time even when a strong acid is used as the acidic substance.

10: double structure container, 11: pressure resistant container (outer container), 12: aerosol valve, 13A: first housing, 13B: second housing, 14A: first stem, 14B: second stem, 15A: first inner bag, 15B: second inner bag, 16: filling space for propellant, 21: actuator, 22A: first actuator passage, 22B: second actuator passage, 23: mixing space, 23A: turning passage, 24: injection port forming member, 24A: discharge port

30: aerosol product, 31a: first outer container, 31b: second outer container, 32a: first inner container, 32b: second inner container, 33a: filling space for first propellant, 33b: for second propellant Filling space, 35: actuator passage, 36: actuator, 37: stationary platen

1: test table, 2: virus application surface, 3: petri dish

Claims (9)

An aerosol product comprising a first container filled with a first liquid, a second container filled with a second liquid, and a propellant, and having a discharge mechanism for discharging and mixing the first liquid and the second liquid,
the first liquid comprises an aqueous chlorite solution;
The second liquid comprises an aqueous acidic substance solution,
An outer container comprising a propellant filling space filled with the propellant, the first container, and the second container, and the first liquid and the second liquid from the first container and the second container. has a discharge mechanism for discharging and mixing
The propellant filling space is formed between the first container, the second container and the outer container,
discharging the first liquid and the second liquid from the first container and the second container, respectively, by the pressure of the propellant;
An aerosol product characterized by generating chlorine dioxide . 2. The aerosol product according to claim 1, wherein the first liquid and the second liquid are mixed inside the ejection mechanism and then ejected in the form of a mist. An aerosol product comprising a first container filled with a first liquid, a second container filled with a second liquid, and a propellant, and having a discharge mechanism for discharging and mixing the first liquid and the second liquid,
the first liquid comprises an aqueous chlorite solution;
the second liquid comprises an acidic substance aqueous solution;
A first inner container filled with the first liquid, a second inner container filled with the second liquid, a first outer container storing the first inner container, and a second inner container storing the second inner container Having two outer containers and a discharge mechanism for discharging and mixing the first liquid and the second liquid,
Spaces formed between the first inner container and the first outer container and between the second inner container and the second outer container are filled with a propellant,
discharging the first liquid and the second liquid from the first container and the second container, respectively, by the pressure of the propellant;
An aerosol product characterized by generating chlorine dioxide. 4. The aerosol product of any one of claims 1-3, wherein the chlorite salt comprises sodium chlorite. The aerosol product according to any one of claims 1 to 4, wherein the acidic substance is at least one selected from the group consisting of hydrochloric acid, sulfuric acid, citric acid and lactic acid. The aerosol product according to any one of claims 1 to 5 , wherein the aqueous chlorite solution has a pH of 5 or more and 12.5 or less. The aerosol product according to any one of claims 1 to 6 , wherein the concentration of the aqueous chlorite solution is 0.1 to 100,000 ppm on a mass basis. The aerosol product according to any one of claims 1 to 7 , wherein the concentration of the acidic substance aqueous solution is 0.1 to 30% by mass. The aerosol product according to any one of claims 1 to 8 , wherein the second liquid contains an additive.

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